Magnetically Enhanced Low Temperature-High Density Plasma-Chemical Vapor Deposition Plasma Source For Depositing Diamond and Diamond-Like Films

ABSTRACT

A magnetically enhanced low temperature high density plasma chemical vapor deposition (LT-HDP-CVD) source has a hollow cathode target and an anode, which form a gap. A cathode target magnet assembly forms magnetic field lines substantially perpendicular to the cathode surface. A gap magnet assembly forms a magnetic field in the gap that is coupled with the cathode target magnetic field. The magnetic field lines cross the pole piece electrode positioned in the gap. The pole piece is isolated from ground and can be connected to a voltage power supply. The pole piece can have negative, positive, floating, or RF electrical potentials. By controlling the duration, value, and sign of the electric potential on the pole piece, plasma ionization can be controlled. Feed gas flows through the gap between the hollow cathode and anode. The cathode can be connected to a pulse power or RF power supply, or cathode can be connected to both power supplies. The cathode target and substrate can be inductively grounded.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No.16/261,516, filed Jan. 29, 2019, which is a continuation application ofU.S. application Ser. No. 15/261,197, filed Sep. 9, 2016, which claimsthe benefit of U.S. Provisional Application No. 62/270,356, filed Dec.21, 2015, the disclosures of which are incorporated by reference hereinin their entireties. U.S. application Ser. No. 15/260,841 entitled“Capacitive Coupled Plasma Source for Sputtering and Resputtering”, U.S.application Ser. No. 15/260,857 entitled “Electrically and MagneticallyEnhanced Ionized Physical Vapor Deposition Unbalanced SputteringSource”, and U.S. application Ser. No. 15/261,119 entitled “MagneticallyEnhanced High Density Plasma-Chemical Vapor Deposition Plasma Source forDepositing Diamond and Diamond-Like Films” are incorporated by referenceherein in their entireties.

BACKGROUND Field

The disclosed embodiments generally relate to a plasma enhanced-chemicalvapor deposition (PE CVD) apparatus and method and, more particularly,relate to a pulse magnetically enhanced low temperature-high densityplasma-chemical vapor deposition (LT-HDP-CVD deposition) apparatus andmethod.

Related Art

Two CVD plasma sources for depositing diamond like coatings and diamondfilms include hot filament chemical vapor deposition (HFCVD) andmicrowave assisted CVD. Both methods require a high temperature on thesubstrate to form a carbon film with a high content of sp3 bonds. Thus,it would be advantageous to develop new LT-HDP-CVD technology that wouldallow the deposition of diamond and DLC films at a much low temperature.

SUMMARY

Various embodiments relate to an apparatus, method, and system for apulse magnetically enhanced low temperature-high density plasma-chemicalvapor deposition (LT-HDP-CVD) deposition of thin and thick filmcoatings, particularly diamond and diamond like coatings. The thicknessof diamond and diamond like coatings can be in a range of 10 Å to 100μm.

The magnetically enhanced LT-HDP-CVD source includes (a) a hollowcathode connected to a power supply, which can be a pulsed power supply,variable power direct current (DC) power supply, radio frequency (RF)power supply, pulsed RF power supply, and/or high power impulsemagnetron sputtering (HIPIMS) power supply, (b) an anode that isconnected to ground, (c) a gap between a hollow cathode and an anode,(d) a row of permanent magnets or electromagnets that are positionedadjacent to the gap in order to form a magnetic field in the gap, (e) acathode magnet assembly configured to generates magnetic field linessubstantially perpendicular to a surface of the hollow cathode, (f) amagnetic coupling between the cathode magnet assembly and a magneticfield in the gap, and (g) a flowing liquid that cools and controls thetemperature of the hollow cathode.

The magnetically enhanced LT-HDP-CVD source may include (a) a pole piecepositioned adjacent to the magnets forming the magnetic field in the gapand exposed to the plasma through the gap, (b) a gas distributionsystem, (c) an inductor connected between the hollow cathode and ground,(d) a motor that rotates the cathode magnet assembly, (e) a voltagepower supply connected with the pole piece, (f) an inductor connectedbetween the pole piece and ground, (g) a RF power and/or pulse powersupply connected to the pole piece, and (h) a RF power and/or pulsepower supply connected to the hollow cathode.

The magnetically enhanced LT-HDP-CVD apparatus includes (a) amagnetically enhanced LT-HDP-CVD source, (b) a vacuum chamber, (c) asubstrate holder, (d) a substrate, (e) a feed gas mass flow controller,and (f) a vacuum pump.

The magnetically enhanced LT-HDP-CVD apparatus may include (a) a directcurrent (DC) or radio frequency (RF) substrate bias power supply, (b) asubstrate heater, (c) a plurality of magnetically enhanced LT-HDP-CVDsources, (d) a gas activation source, (a) an additional magnet assemblypositioned between the magnetically enhanced LT-HDP-CVD plasma sourceand the substrate holder or positioned below the substrate holder insideor outside a vacuum chamber.

A method of providing magnetically enhanced LT-HDP-CVD thin filmdeposition includes (a) forming a magnetic field in the gap between ahollow cathode and an anode, (b) forming magnetic field linesperpendicular to a bottom surface of the hollow cathode, (c) positioningsubstrate, (d) providing feed gas, (e) applying negative voltage to thecathode, and (e) igniting volume plasma discharge.

The method of providing magnetically enhanced LT-HDP-CVD thin filmdeposition may include (a) applying heat to the substrate, (b) applyingbias voltage to the substrate, (c) applying voltage to the pole piece,(d) applying pulse voltage to the cathode, (e) synchronizing pulsevoltage applied to the pole piece and pulse voltage applied to thecathode target, (f) inductively grounding the substrate, (g) inductivelygrounding the cathode, (h) supplying feed gas through a gas activationsource, and (i) inductively grounding the cathode, inductively groundingthe pole piece.

A magnetically enhanced low temperature-high density plasma-chemicalvapor deposition (LT-HDP-CVD) apparatus includes a hollow cathodeassembly; an anode positioned on top of the hollow cathode targetassembly, thereby forming a gap between the anode and the hollow cathodeassembly; a cathode magnet assembly; a row of magnets that generate amagnetic field in the gap and a magnetic field on the hollow cathodesurface with the cathode magnet assembly such that magnetic field linesare substantially perpendicular to the hollow cathode assembly; a powersupply that generates a train of negative voltage pulses that generatesa pulse electric field in the gap perpendicular to the magnetic fieldlines, the pulse electric field igniting and sustaining plasma during apulse, a frequency, duration, and amplitude of the train of negativevoltage pulses being selected to increase a degree of dissociation ofthe feed gas molecules atoms.

The apparatus may include a pole piece positioned adjacent to the gapand connected to the power supply, and a radio frequency (RF) powersupply s connected to the hollow cathode assembly, wherein the RF powersupply generates output voltage with a frequency in a range of about 1MHz to 100 MHz. The apparatus may include a substrate holder, and an RFsubstrate bias power supply connected to the substrate holder. Theapparatus may include an inductor connected between the substrate holderand ground. The apparatus may include a substrate holder, and asubstrate bias power supply connected to the substrate holder, whereinthe substrate bias power supply generates a bias voltage on thesubstrate in a range of about −10 V to −2000 V. The magnetic field inthe gap may be in a range of about 50 G to 5000 G. The cathode magneticarray may be rotatable.

A method of magnetically enhanced low temperature-high densityplasma-chemical vapor deposition (LT-HDP-CVD) includes providing ahollow cathode; forming a gap between the hollow cathode and an anode;positioning a cathode magnet assembly; generating a magnetic field inthe gap such that magnetic field lines are substantially perpendicularto the hollow cathode surface; positioning a pole piece in the gap;providing a pulse power to the cathode target that ignites and sustainsvolume discharge; and generating a train of negative voltage pulses,wherein a frequency, duration, and amplitude of the train of negativevoltage pulses being selected to increase a degree of dissociation andionization of feed gas molecules and atoms.

The method may use a power supply connected to the pole piece, and mayinclude connecting an RF power supply to the hollow cathode, andgenerating output voltage using the RF power supply with a frequency ina range of about 1 MHz and 100 MHz.

The power supply may generate an output voltage with a value in a rangeof about −100 V to −3000 V, and the method may include connecting asubstrate bias power supply to a substrate holder, and generating biasvoltage on the substrate in a range of about −10 V to −2000 V. Themagnetic field in the gap may be in a range of about 50 G to 10000 G,and the cathode target material may include carbon.

Other embodiments will become apparent from the following detaileddescription considered in conjunction with the accompanying drawings. Itis to be understood, however, that the drawings are designed as anillustration only and not as a definition of the limits of any of theembodiments.

BRIEF DESCRIPTION OF THE DRAWINGS

The following drawings are provided by way of example only and withoutlimitation, wherein like reference numerals (when used) indicatecorresponding elements throughout the several views, and wherein:

FIG. 1(a) shows an illustrative cross-sectional view of an embodiment ofa magnetically enhanced LT-HDP-CVD source;

FIG. 1(b) shows an illustrative cross-sectional view of magnetic fieldlines for the magnetically enhanced LT-HDP-CVD source shown in FIG.1(a);

FIG. 1(c) shows a timing diagram of negative voltage pulses generated bya pulse power supply and applied to a pole piece from the LT-HDP-CVDsource;

FIG. 1(d) shows a timing diagram of negative RF voltages applied to acathode target when negative pulses are applied to the pole piece fromthe LT-HDP-CVD source;

FIG. 1(e) shows a timing diagram of negative voltage pulses withdifferent amplitudes that can be generated by a pulse power supply andapplied to the pole piece from the LT-HDP-CVD source;

FIG. 1 (f) shows a timing diagram of negative RF voltages applied to thecathode target when negative voltage pulses with different amplitudesare applied to the pole piece from the LT-HDP-CVD source;

FIG. 1 (g) shows a timing diagram of negative voltage pulses withdifferent frequencies that can be generated by a pulse power supply andapplied to the pole piece from the LT-HDP-CVD source;

FIG. 1 (h) shows a timing diagram of negative RF voltages applied to thecathode target when negative voltage pulses with different frequenciesare applied to the pole piece from the LT-HDP-CVD source;

FIG. 1 (i) shows a timing diagram of negative voltage pulses that can begenerated by a pulse power supply and applied to the pole piece from theLT-HDP-CVD source;

FIG. 1 (j) shows a timing diagram of negative RF voltages applied to aninductively grounded cathode when negative voltage pulses with differentfrequencies are applied to the pole piece from the LT-HDP-CVD source;

FIG. 2 shows an illustrative cross-sectional view of an embodiment for amagnetically enhanced LT-HDP-CVD source;

FIG. 3 shows a timing diagram of negative voltage pulses that can begenerated by a pulse power supply and applied to the pole piece;

FIGS. 4 (a, b, c, d) show timing diagrams of negative voltage pulsesthat can be generated by a pulse power supply and applied to the cathodeassembly;

FIGS. 5 (a, b) show timing diagrams of RF voltages that can be appliedto the cathode assembly;

FIGS. 5 (c, d) show timing diagrams of RF voltages and pulse voltagesthat can be applied to the cathode assembly;

FIGS. 6 (a, b, c, d) show timing diagrams of different shapes of voltagepulses that can be applied to the cathode assembly;

FIG. 6 (e) shows a timing diagram of RF voltage that can be applied tothe inductively grounded cathode assembly;

FIG. 7 (a) shows an illustrative cross-sectional view of an embodimentof a magnetically enhanced LT-HDP-CVD system for thin film deposition;

FIG. 7 (b) shows an illustrative cross-sectional view of a multilayeredfilm;

FIG. 8 shows an illustrative cross-sectional view of an embodiment of amagnetically enhanced LT-HDP-CVD system having two rectangularLT-HDP-CVD sources;

FIG. 9 shows an illustrative cross-sectional view of an embodiment of amagnetically enhanced LT-HDP-CVD source and processes for applying acoating on a razor blade tip; and

FIG. 10 shows a block diagram of at least a portion of an exemplarymachine in the form of a computing system that performs methodsaccording to one or more embodiments disclosed herein.

It is to be appreciated that elements in the figures are illustrated forsimplicity and clarity. Common but well-understood elements that areuseful or necessary in a commercially feasible embodiment are not shownin order to facilitate a less hindered view of the illustratedembodiments.

DETAILED DESCRIPTION

Embodiments of a magnetically enhanced low temperature-high densityplasma-chemical vapor deposition (LT-HDP-CVD) deposition source, whencompared with conventional PE-CVD, have unique magnetic field geometryas shown in FIG. 1 (a). This geometry, on one side, forms a magneticfield in a gap between an anode and a hollow cathode and, on anotherside, forms magnetic field lines that cross a surface of the cathodesubstantially perpendicularly to the cathode surface. Therefore,magnetic field lines from one side terminate on the cathode surface, andfrom another side terminate in the gap on a pole piece that does nothave the same potential as a cathode. This magnetic field geometry doesnot confine electrons near the cathode target surface. Rather, thismagnetic field geometry allows electrons to move from the cathodesurface toward the gap between the cathode and the anode. During thismovement, the electrons dissociate the feed gas molecules, and ionizeatoms. By the time these electrons come in contact with the pole piecein the gap, which concentrates the magnetic field in the gap, theseelectrons have lost a portion of their initial energy. A portion of theelectrons drift back to the hollow cathode surface due to a magneticmirror effect or a presence of negative potential on the pole piece. Ifelectrons reach the hollow cathode surface during the time betweenvoltage pulses when the hollow cathode voltage is equal to zero, theseelectrons discharge a positive charge on top of the cathode surface andsignificantly reduce or eliminate the probability of arcing on thecathode target surface during the LT-HDP-CVD process. The positivecharge on the hollow cathode target surface can be formed due to theformation of low electrical conductivity films during the LT-HDP-CVDprocess. The amount of electrons returning to the hollow cathode surfacecan be controlled by selecting the magnetic field geometry, gaspressure, amplitude, duration, and distance between applied voltagepulses, and/or the duration and value of negative potential on the polepiece.

The magnetically enhanced LT-HDP-CVD source 100 has a hollow cathode 101and an anode 102 that forms a gap 103 as shown in FIG. 1 (a). The hollowcathode has a magnetic assembly 104 positioned behind the hollow cathode101. The magnetic assembly 104 can be stationary, rotatable, or movable.The magnetic assembly can include magnets and magnetic pole pieces.Magnetic field lines 105 are substantially perpendicular to the hollowcathode surface. The gap 103 has a magnet assembly comprising a row ofmagnets 106 and a pole piece 107. This pole piece 107 can be made frommagnetic or nonmagnetic material. If the pole piece 107 is made frommagnetic material, the pole piece 107 concentrates the magnetic field,which can increase a magnetic mirror effect for the electrons driftingfrom the cathode surface 101 towards the gap 103. The pole piece 107 isexposed to the plasma through the gap 103. The pole piece 107 andmagnets 106 are positioned on supporter 108. The pole pieces 107 can beconnected to voltage power supply 109 or can be grounded or isolatedfrom ground. In some embodiments, pole piece 107 can be inductivelygrounded through inductor 118 and switch 119. In some embodiments, powersupply 109 is an RF power supply that generates voltage with frequenciesin a range 100 kHz to 100 MHz. Pole piece 107 is isolated from thesupporter 108 and magnets 106 by isolators 110. The cathode is connectedto power supply 111. The cathode can be also connected to another powersupply 112 through switch 113. In some embodiments, power supply 111 isa radio frequency (RF) power supply and power supply 117 is a pulsepower supply. These power supplies generate an RF—pulse superimposeddischarge. In some embodiments only the RF power supply 111 isconnected\to the cathode 101. In this case, the cathode 101 can beinductively grounded through inductor 114 and switch 115. If the cathodetarget is inductively grounded, RF discharge cannot generate a constantnegative voltage bias and there is sputtering from the cathode does notoccur. In some embodiments, only one power supply 112 is connected tothe cathode 101 and generates negative voltage pulses. Magnetic fieldlines 105 guide the electrons from the hollow cathode surface toward agap between the anode and the hollow cathode as shown in FIG. 1 (b) byarrow 116. By the time the emitted electrons arrive at the gap, aportion of their initial energy has been lost due to dissociation,ionization, and/or elastic and/or non-elastic collisions with neutralatoms, molecules ions, and/or other electrons from the feed gas. Oneportion of the electrons reflect from point “A” due to a magnetic mirroreffect and another portion of the electrons reflect from point “B” dueto the presence of a negative potential on pole piece 107. If pole piece107 has a ground potential, electrons are absorbed. Therefore, bycontrolling the electrical potential on pole piece 107, the plasmadensity near the cathode can be controlled. Plasma density controls thedegree of feed gas dissociation and ionization. The electrons drift backfrom the gap towards the hollow cathode surface as shown by arrow 117. Anegative voltage on the pole piece 107 is preferably less than −50 V inorder to prevent possible sputtering from the pole piece 107. In someembodiments, negative voltage pulses with a duration in a range of 5-100μs, amplitude of 100-2000 V, and a frequency of up to about 100 kHz areapplied to the pole piece 107. The voltage pulse can be triangular,rectangular, trapezoidal, or any other shape. Voltage pulses can benegative, bipolar, or positive. The application of negative high voltagepulses increase the energy of the electrons reflected from the polepiece 107 and, therefore, the plasma density. FIG. 1 (c) shows negativevoltage pulses generated by power supply 109 when cathode target fromLT-HDP-CVD source is connected to RF power supply 111. Pulse negativevoltage increases electron energy in RF discharge and, therefore,increases plasma density. As a result, in some embodiments, the negativevoltage bias generated by RF power supply 111 is reduced during thepulse from U_(D) ² to U_(D) ¹ as shown in FIG. 1 (d). FIG. 1 (e) showsnegative voltage pulses with different amplitude U¹-U³ generated bypower supply 109. Pulse voltage increases the amount of electrons and,therefore, increases the plasma density. A greater negative pulsevoltage amplitude U³ generates greater plasma density and, therefore,will requires a less negative voltage bias U_(D) ¹ generated by the RFpower supply. As a result, in some embodiments, the discharge voltagegenerated by RF power supply 111 is reduced during the pulse as shown inFIG. 1 (f). In some embodiments, the influences of the frequency of thenegative voltage pulses generated by power supply 109 on dischargevoltage generated by RF power supply 111 or 118 is shown in FIGS. 1 (g,h). FIG. 1 (g) shows negative voltage pulses with different frequenciesgenerated by power supply 109. As a result, in some embodiments, thedischarge voltage generated by RF power supply 111 is reduced during thepulses as shown in FIG. 1 (h). FIG. 1 (i) shows negative voltage pulsesgenerated by power supply 109. As a result, in some embodiments, thepeak-to-peak voltage U_(pp) ¹ generated by RF power supply 111 connectedto the inductively grounded cathode target 101 is reduced during thepulse U_(pp) ² as shown in FIG. 1 (j). Depending on the voltageamplitude, duration, and shape of the voltage pulses applied to thehollow cathode 101 and the voltage applied to the pole piece 107 andfeed gas pressure, the electrons move back and forth between the cathodetarget and the gaps.

FIG. 2 shows a cross-sectional view of an embodiment of the magneticallyenhanced LT-HDP-CVD deposition source 200. The magnetically enhancedLT-HDP-CVD deposition source 200 includes a base plate 201. The baseplate has an electrical ground potential. The cathode assembly includesa water jacket 202 and a hollow cathode 203. The water jacket 202 iselectrically isolated from the base plate 201 with isolators 204. Wateror another fluid for cooling can move inside the water jacket 202through inlet 205, and can move outside the water jacket 202 throughoutlet 206. The hollow cathode 207 is positioned on top of water jacket202. The hollow cathode 203 is electrically connected to power supply207 through a water inlet 205, transmission line 208, and switch 209.The power supply 207 can include a direct current (DC) power supply, apulsed power supply that generates unipolar negative voltage pulses, apulsed power supply that generates asymmetrical bipolar voltage pulses,a pulsed power supply that generates symmetrical bipolar voltage pulses,an RF power supply, and/or a high power pulsed power supply. Any ofthese power supplies can generate different shapes, frequencies, andamplitudes of voltage pulses. These power supplies can work in powercontrol mode, voltage control mode, or current control mode. The waterinlet 206 is electrically connected to a power supply 210 through atransmission line 211, matching network 212, and a switch 213. A powersupply 210 can include a radio frequency (RF) power supply, pulsed RFpower supply, high frequency (HF) power supply, pulsed HF power supply,or any combination of these supplies. The frequency can be in the rangeof 100 kHz to 100 MHz. Power supply 210 can operate together with powersupply 207 or can operate alone without connecting power supply 207 tothe cathode assembly. Power supply 207 can operate together with powersupply 210 or can operate alone without connecting power supply 210 tothe cathode assembly. The hollow cathode 203 can be powered with anycombination of the power supplies mentioned above. All of theabove-mentioned power supplies can operate in current control mode,voltage control mode, and/or power control mode. Power supply 207 andpower supply 210 can be connected to the same water inlet 205. Thecathode 203 is formed in the shape of a round hollow shape, but can beformed in other shapes, such as a rectangular hollow shape, disc, andthe like. The hollow cathode 203 material can be conductive,semi-conductive, and/or non-conductive. The following chemical elements,can be used as a cathode material: B, C, Al, Si, P, S, Ga, Ge, As, Se,In, Sn, Sb, Te, I, Tl, Pb, Bi, Sc, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y,Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Lu, Hf, Ta, W, Re, Os, Ir, Pt, Au,La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Be, Mg, Ca, Sr,and/or Ba. A combination of these chemical elements or their combinationwith gases O₂, N₂, F, Cl, and/or H₂ can also be used as a cathodematerial. Power supplies 207, 210, and switches 209, 213 can beconnected to the controller 214 and computer 215. Controller 214 and/orcomputer 215 control the output voltage values and timing of the powersupplies 207 and 210. The power supplies 207 and 210 can besynchronized.

The cathode assembly includes a stationary cathode magnetic assembly 216positioned inside the water jacket 202. The cathode magnetic assembly216 in an embodiment includes a plurality of magnets 217. The magneticassembly 216 is mounted on a plate 218 that is made from non-magneticmaterial. The presence of magnets 217 provides for a perpendiculardirection of the magnetic field lines to the surface of the cathode 203.In an embodiment, the cathode magnetic assembly 216 (stationary orrotatable) includes a plurality of permanent magnets and magnetic polepieces. In an embodiment, the magnetic assembly 216 is rotatable. In anembodiment, the magnetic assembly 216 is kidney-shaped. The magneticassembly 216 can rotate with a speed in the range of 1-500 revolutionsper minute.

A ring-shaped anode 219 is positioned proximate to the hollow cathode203. The anode 219 and the hollow cathode 203 form a circular gap 220.The electric field lines are perpendicular to the magnetic field linesin the gap 220. Magnetic field lines 221 are substantially perpendicularto the cathode surface 203. In embodiment a feed gas is fed through thegap 220 between the hollow cathode 203 and the anode 219.

A magnet assembly that generates magnetic field 222 is positioned aroundthe gap 220. The magnetic assembly includes magnetic ring-shaped polepieces 223 and a plurality of permanents magnets 224. The magnets 224are positioned inside the magnet housing (not shown in FIG. 2). Thevalue of the magnetic field in the gap 220 caused by the permanentsmagnets 224 is in a range of 100-10000 G. The pole piece 223 and magnets224 are mounted on top of the support 225.

Power supplies 207 and 210 are connected to the controller 214.Controller 226 can be connected to a computer 215. Controller 214controls the output voltage signals from the power supplies 207, 212.

The pole piece 223 is electrically isolated from the magnet 224 byisolator 229. The pole piece 223 is electrically isolated from thesupport 225 by isolator 219.

The magnetic fields 222 and are shaped to provide electron movementbetween the hollow cathode 203 and pole piece 223. During this movement,electrons dissociate and ionize feed gas molecules and/or atoms andsputtered target material atoms.

Pole piece 223 is connected to voltage control mode power supply 233through electrode 231 and transmission line 230. Electrode 231 isisolated from the base plate by isolator 232. In an embodiment, themagnets 213, 212 are electromagnets. In embodiment power supply 233 isRF power supply. In embodiment pole piece 223 can be grounded throughinductor.

FIG. 3 shows voltage pulse shapes that can be generated by power supply233. The amplitude of negative voltage pulses can be in the range of 100to 2500 V. The pulse duration can be in the range of 1 to 50 μs.

FIGS. 4 (a, b, c, d) show different voltage pulse shapes, amplitudes,and frequencies that power supply 207 can provide. Typically, in orderto generate and sustain volume discharge, the power supply 207 operatesin power control mode or in voltage control mode. FIG. 4 (a) shows acontinuous train of triangular negative voltage pulses. The amplitudecan be in the range of 100-3000 V. FIG. 4 (b) shows a train of negativevoltage pulses that has different voltage amplitudes. The voltage pulseswith amplitude V1 can be optimized to increase the dissociation rate offeed gas molecules, and voltage pulses with amplitude V2 can beoptimized to increase the ionization rate of the atoms, in particularcarbon atoms. The pulse voltage provides energy to the electrons in theplasma discharge. For example, voltage V1 is optimized to increase thedissociation rate of gas molecules containing carbon atoms, such asC₂H₂, CH₄, CO, CO₂, C₃H₈, CH₃OH, C₂H₅OH, CH₃Cl, and the like. Also, itis important to increase the dissociation rate of H₂ (H₂+e→H₂*+e→H+H+e).The high-voltage pulse amplitude V2 provides more energy to theelectrons. Electrons collide with gas molecules, gas atoms, and targetmaterial atoms. Typically, gas atoms need more energy in order to beionized and molecules need less energy to dissociate. That is, if thevoltage amplitude is high then the probability of ionization of atomswill be high. The pulse duration can be in the range of 1 microsecond to1 millisecond. FIG. 4 (c) shows a pulse train of triangular negativevoltage pulses. The duration of the train of negative voltage pulses canbe in the range of 100 microseconds to 10 milliseconds. The frequency ofthe train of negative voltage pulses can be in the range of 100 Hz to 20KHz. FIG. 4 (d) shows a continuous voltage that can be in the range of−100 to −2000 V.

FIG. 5 (a) and FIG. 5 (b) show continuous and pulse RF voltages that canbe provided by power supply 210. The RF power can be in the range of 100W to 10 kW. The RF frequency can be in the range of 100 kHz to 100 MHz.The frequency of RF pulses can be in the range of 100 Hz to 100 KHz.FIG. 5 (c) shows voltage on the hollow cathode 203 when power supply 210provides a continuous train of triangular voltage pulses and powersupply 210 simultaneously provides continuous RF voltage. FIG. 5(d)shows voltage on the cathode when power supply 207 provides a train oftriangular voltage pulses and power supply 210 simultaneously providespulse RF voltages. Power supply 233 can generate a continuous train ofrectangular negative voltage pulses as shown in FIG. 6 (a). Power supply233 can generate a pulse train of rectangular negative voltage pulses asshown in FIG. 6 (b). The duration of the pulse train of voltage pulsescan be in the range of 100 μs to 10 ms. FIG. 6 (c) shows differentvoltage pulse shapes in one pulse train. FIG. 6 (d) shows a train ofasymmetric bi-polar voltage pulses when negative pulse voltage has atriangular shape. FIG. 6 (e) shows continuous RF voltages generated bypower supply 210 on the inductively grounded hollow cathode 203.

The magnetically enhanced LT-HDP-CVD deposition source 200 can bemounted inside the vacuum chamber 201 in order to construct themagnetically enhanced LT-HDP-CVD apparatus 291 as shown in FIG. 7 (a).The vacuum chamber 270 contains feed gas and plasma. The vacuum chamber270 is coupled to ground 288. The vacuum chamber 270 is positioned influid communication with a vacuum pump 287, which can evacuate the feedgas from the vacuum chamber 270. Typical baseline pressure in the vacuumchamber 270 is in a range of 10⁻⁵ to 10⁻⁹ Torr.

A feed gas is introduced into the vacuum chamber 270 through a gas inlet289 from a feed gas source. A mass flow controller 280 controls gas flowto the vacuum chamber 270. In an embodiment, vacuum chamber 270 has manygas inlets and mass flow controllers. The gas flow can be in a range of1 to 1000 SCCM depending on plasma operating conditions, pumping speedof the vacuum pump 287, process conditions, and the like. In someembodiments, the feed gas is introduced through the gap 220 shown inFIG. 2 using the magnetically enhanced LT-HDP-CVD 200. Typical gaspressure in the vacuum chamber 270 during a CVD process can be in arange of 0.1 mTorr to 50 Torr. In an embodiment, a plurality of gasinlets and a plurality of mass flow controllers sustain a desired gaspressure during the CVD process. The plurality of gas inlets andplurality of mass flow controllers may be positioned in the vacuumchamber 270 at different locations. The feed gas can be a noble gas,such as Ar, Ne, Kr, Xe; a reactive gas, such as N₂, O₂; or any other gasthat is suitable for CVD processes. For depositing DLC or diamond films,the feed gas contains atoms of carbon. For example, the cathode targetmaterial can be carbon. The feed gas can be C₂H₂, or CH₄ or any othergas/vapor containing carbon atoms, such as CO, CO₂, C₃H₈, CH₃OH, C₂H₅OH,and CH₃Cl. The feed gas can also be a mixture of different of gases. Insome embodiments, the cathode target material is not a carbon. In someembodiments, the cathode target material is carbon. The LT-HDP-CVDsource is connected to power supply 207 through water inlet 205, andpower supply 210 with matching network 212 are connected to water outlet206. In some embodiments, only power supply 207 is connected to theLT-HDP-CVD source. In some embodiments only power supply 210 isconnected to the LT-HDP-CVD source.

The magnetically enhanced LT-HDP-CVD apparatus 291 includes a substratesupport 284 that holds a substrate 283 or other work piece for plasmaprocessing. The substrate support 284 is electrically connected to biasvoltage power supply 290 through connector 285. The bias voltage powersupply 290 can include a radio frequency (RF) power supply, alternatingcurrent (AC) power supply, very high frequency (VHF) power supply,and/or direct current (DC) power supply. The bias power supply 290 canoperate in continuous mode or in pulse mode. The pulse substrate biasvoltage can be synchronized with pulse voltage applied to the cathode203. The bias power supply 290 can be a combination of different powersupplies that can provide different voltage oscillation frequencies. Thenegative bias voltage on the substrate 283 can be in a range of −1 to−2000 V. The negative substrate bias voltage can attract positive ionsto the substrate 283. In some embodiments, substrate holder 284 isinductively grounded through switch 292 and inductor 293 and isconnected to RF power supply 286. During operation, there is no negativeconstant bias. There are only RF voltage oscillations on a surface ofthe substrate 283 that promote dissociation and ionization of the carboncontaining gas. In some embodiments, switch 292 closes and opens with afrequency of 1 Hz to 100 kHz. When switch 292 is open, the RF voltagebias is present and ions bombard the growing film. When switch 292 isclosed, the RF voltage bias is equal to zero and ions are not bombardingthe growing film. In some embodiments, switch 292 can be repetitivelyclosed during the time in a range of 1 sec to 100 sec. In someembodiments, switch 292 can be repetitively opened in a range of 1 secto 100 sec. Closing and opening switch 292 allows a multilayered film tobe formed in which layers have different microstructures. In someembodiments, layers (1) and layers (2) have different concentrations ofsp3 bonds as shown in FIG. 7 (b). The substrate support 284 can includea heater that is connected to a temperature controller. The temperaturecontroller regulates the temperature of the substrate 283. In anembodiment, the temperature controller controls the temperature of thesubstrate 283 to be in a range of −20 C to (+1200) C.

An additional magnet assembly between LT-HDP-CVD source 200 andsubstrate 283 can be positioned inside the chamber 270 or outside thechamber 270 in order to increase plasma density near the substrate and,therefore, increase the dissociation rate of the gas molecules andimprove film uniformity on the substrate. Power supplies 207, 210, 233,286, 290 can be connected to the controller 214 and computer 215.

The magnetically enhanced LT-HDP-CVD source can be positioned in thevacuum chamber 301 as shown in FIG. 8. Two rectangular magneticallyenhanced LT-HDP-CVD sources 304 and 305 are positioned inside the vacuumchamber 301. Vacuum pump 302 can provide a base pressure up to 10⁻⁸Torr. Two heaters 308, 309 control temperature of the substrate 307. Tworectangular magnetically enhanced LT-HDP-CVD sources 304, 305 areconnected to power supplies 318, 316 and 317, 312 respectively.LT-HDP-CVD source 305 is connected to RF power supply 318 through switch319 and connected to ground through inductor 321 and switch 320.LT-HDP-CVD source 305 is connected to pulse power supply 315 throughswitch 316. Pole piece 223 from LT-HDP-CVD source 305 is connected topower supply 324 through switch 325 and electrode 231. LT-HDP-CVD source304 is connected to RF power supply 317 through switch 327 and isconnected to ground through inductor 328 and switch 329. LT-HDP-CVDsource 304 is connected to pulse power supply 312 through the switch311. The pole piece 223 from LT-HDP-CVD source 304 is connected to powersupply 323 through switch 322 electrode 231. Substrate holder 306 isconnected to bias power supply 313. Power supplies 313, 318, 324, 315,312, 317, 323 and switches 325, 319, 316, 320, 311, 322, 329, 327 areconnected to controller 314. Power supplies 315, 312 can provide anyvoltage pulses in any order as shown in FIGS. 4 (a, b, c, d), FIGS. 5(a, b, c, d), and FIGS. 6 (a, b). Power supplies 318, 317 can provide RFvoltage as shown in FIGS. 4 (a, b, c, d), FIGS. 5 (a, b, c, d), andFIGS. 6 (a, b). Bias power supply 313 can be an RF power supply with afrequency in a range of 500 kHz to 30 MHz. Bias power supply 313 can bea DC power supply or pulse DC power supply. Power supplies 318, 315,312, 313, 317, 324, 323 can be connected to controller 314.

The substrate support 306 can provide for rotation of the substrate 307.The substrate support 306 can have different parts that rotate atdifferent speeds. The substrate support 306 can hold one or moresubstrates 307 or work pieces.

In an embodiment, the substrate 307 is a part of an automobile engineand the coating is a hydrogenated diamond-like coating (DLC). In anembodiment, the substrate 307 is a part of an automobile engine and thecoating is hydrogenated diamond-like coating (DLC). The DLC coatingreduces a coefficient of friction of moving parts in the automobileengine. The thickness of the DLC coating is in a range of 0.1 to 10 mkmdepending on the particular engine part. The parts that can be coatedinclude the turbocharger, valve, piston, piston ring, piston pin, heatexchanger, connecting rod, crank end bearing, bearing, ball from anybearing, after cooler, intercooler, rocker arm, injector, valve guide,push rod, camshaft, fuel injection pump, oil pump, or any other partassociated with the automobile engine.

The method of LT-HDP-CVD depositing film on the substrate includes thefollowing steps. A first step is cleaning the surface of the substrateby a sputter etch process with a noble gas. In this step, the feed gaswill be a noble gas, such as Ar. The gas pressure can be in a range of 1to 20 mTorr. The substrate bias can be between −300 V and −1000 V.Magnetically enhanced CVD sources 305 operate in sputter etch mode. Inthis mode, only RF power supplies 318 and 317 are connected to thecathode from LT-HDP-CVD source 305 and/or 304. The cathodes of theLT-HDP-CVD sources 305, 304 are inductively grounded in order to preventsputtering from the cathode. RF power supplies generate RF power in arange of 1 to 10 kW. In some embodiments, cathodes from LT-HDP-CVDsources are only connected to pulse power supplies 315, 312. Powersupplies 315, 312 generate voltage pulses with amplitude, duration, andfrequency selected to provide optimum energy in a range of 150 eV to theelectrons to generate Ar ions.

A second step is reactive ion etch (RIE) cleaning of the surface of thesubstrate using a reactive gas, such as O₂ or H₂. In some embodiments,the cleaning is made with H₂. The gas pressure can be in the range of 1mTorr to 100 mTorr. The substrate bias can be between −100 V and −1000V. Magnetically enhanced LT-HDP-CVD sources 305 and 304 are operated inRIE mode. In this mode, only RF power supplies 318 and/or 317 areconnected to LT-HDP-CVD source 305 and/or 304. The cathode fromLT-HDP-CVD source 305 is inductively grounded. Power supply 312generates RF discharge. Power supply 324 generates voltage pulses withan amplitude, duration, and frequency selected to provide optimum energyin the range of 150 eV to the electrons to generate reactive gas ions.The voltage pulse duration can be in the range of 3-50 μs. For example,the amplitude of the voltage oscillations can be in the range of 300 to1000 V in order to increase the ionization rate of gas atoms. Thevoltage pulse duration can be in the range of 3-8 microseconds. In anembodiment, only the RF power supply 312 operates and the RF power levelis optimized by adjusting output power to provide an optimum amount ofenergy for the electrons in order to maximize the probability ofgenerating atomic hydrogen when electrons collide with hydrogenmolecules. In an embodiment, power supplies 312, 317 operatesimultaneously to generate atomic hydrogen. The third step is filmdeposition. In this step, any gas that includes carbon atoms, such asacetylene, methane, and the like can be used. The substrate temperatureis in the range of about 400 C.

In an embodiment, the work piece is a part of a jet engine, and thecoating can be hydrogenated DLC or hydrogenated metal-doped DLC.

In an embodiment, the magnetically enhanced LT-HDP-CVD source can beused to form hard DLC coating on the tip of a razor blade, as shown inFIG. 9. A blade 403 and magnetically enhanced LT-HDP-CVD source 401 arepositioned inside a vacuum chamber 406. A feed gas, such as Ar, C₂H₂,CH₄, or any other gas that contains carbon atoms, is used for theLT-HDP-CVD process. Power supply 402 provides negative voltage pulses tothe cathode 203 from LT-HDP-CVD, as shown in FIG. 2 and FIG. 9, with aspecified voltage amplitude, pulse duration and frequency. Theparameters of the voltage pulses are shown in FIGS. 4(a, b, c, d), FIGS.5 (a, b, c, d), FIGS. 6 (a, b, c, d). Power supply 404 provides anegative bias voltage on the blade in the range of −20 V to (−200V).Power supply 408 is connected to the pole piece 223 as shown in FIG. 2and FIG. 9. Power supply 408 provides voltage pulses to increaseelectron energy and increase ionization degree of carbon atoms. Powersupply 407 generates RF power and is connected to the cathode 203 fromLT-HDP-CVD as shown in FIG. 2 and FIG. 9. In some embodiments, onlypower supply 402 is connected to the cathode 203. The voltage pulseshapes and voltage pulse frequency from power supply 402 are optimizedin order to obtain a DLC film with hardness in the range of 20-30 GPa.In some embodiments, only power supply 407 is connected to the cathode203. The RF power from power supply 407 is optimized in order to obtaina DLC film with hardness in the range of 30-40 GPa.

The magnetically enhanced LT-HDP-CVD source can be used for manydifferent applications. The deposition of diamond and DLC coatings witha CVD source include, but are not limited to, smart phones, tablets,flat panel displays, hard drives, read/write heads, hair removal,optical filters, watches, valves, facets, thin film batteries, disks,microelectronics, hard masks, transistors, manufacturing mono and polycrystal substrates, and the like. The magnetically enhanced LT-HDP-CVDplasma source can be configured for sputtering applications.

One or more embodiments disclosed herein, or a portion thereof, may makeuse of software running on a computer or workstation. By way of example,only and without limitation, FIG. 10 is a block diagram of an embodimentof a machine in the form of a computing system 900, within which is aset of instructions 902 that, when executed, cause the machine toperform any one or more of the methodologies according to embodiments ofthe invention. In one or more embodiments, the machine operates as astandalone device; in one or more other embodiments, the machine isconnected (e.g., via a network 922) to other machines. In a networkedimplementation, the machine operates in the capacity of a server or aclient user machine in a server-client user network environment.Exemplary implementations of the machine as contemplated by embodimentsof the invention include, but are not limited to, a server computer,client user computer, personal computer (PC), tablet PC, personaldigital assistant (PDA), cellular telephone, mobile device, palmtopcomputer, laptop computer, desktop computer, communication device,personal trusted device, web appliance, network router, switch orbridge, or any machine capable of executing a set of instructions(sequential or otherwise) that specify actions to be taken by thatmachine.

The computing system 900 includes a processing device(s) 904 (e.g., acentral processing unit (CPU), a graphics processing unit (GPU), orboth), program memory device(s) 906, and data memory device(s) 908,which communicate with each other via a bus 910. The computing system900 further includes display device(s) 912 (e.g., liquid crystal display(LCD), flat panel, solid state display, or cathode ray tube (CRT)). Thecomputing system 900 includes input device(s) 914 (e.g., a keyboard),cursor control device(s) 916 (e.g., a mouse), disk drive unit(s) 918,signal generation device(s) 920 (e.g., a speaker or remote control), andnetwork interface device(s) 924, operatively coupled together, and/orwith other functional blocks, via bus 910.

The disk drive unit(s) 918 includes machine-readable medium(s) 926, onwhich is stored one or more sets of instructions 902 (e.g., software)embodying any one or more of the methodologies or functions herein,including those methods illustrated herein. The instructions 902 mayalso reside, completely or at least partially, within the program memorydevice(s) 906, the data memory device(s) 908, and/or the processingdevice(s) 904 during execution thereof by the computing system 900. Theprogram memory device(s) 906 and the processing device(s) 904 alsoconstitute machine-readable media. Dedicated hardware implementations,such as but not limited to ASICs, programmable logic arrays, and otherhardware devices can likewise be constructed to implement methodsdescribed herein. Applications that include the apparatus and systems ofvarious embodiments broadly comprise a variety of electronic andcomputer systems. Some embodiments implement functions in two or morespecific interconnected hardware modules or devices with related controland data signals communicated between and through the modules, or asportions of an ASIC. Thus, the example system is applicable to software,firmware, and/or hardware implementations.

The term “processing device” as used herein is intended to include anyprocessor, such as, for example, one that includes a CPU (centralprocessing unit) and/or other forms of processing circuitry. Further,the term “processing device” may refer to more than one individualprocessor. The term “memory” is intended to include memory associatedwith a processor or CPU, such as, for example, RAM (random accessmemory), ROM (read only memory), a fixed memory device (for example,hard drive), a removable memory device (for example, diskette), a flashmemory and the like. In addition, the display device(s) 912, inputdevice(s) 914, cursor control device(s) 916, signal generation device(s)920, etc., can be collectively referred to as an “input/outputinterface,” and is intended to include one or more mechanisms forinputting data to the processing device(s) 904, and one or moremechanisms for providing results associated with the processingdevice(s). Input/output or I/O devices (including but not limited tokeyboards (e.g., alpha-numeric input device(s) 914, display device(s)912, and the like) can be coupled to the system either directly (such asvia bus 910) or through intervening input/output controllers (omittedfor clarity).

In an integrated circuit implementation of one or more embodiments ofthe invention, multiple identical die are typically fabricated in arepeated pattern on a surface of a semiconductor wafer. Each such diemay include a device described herein, and may include other structuresand/or circuits. The individual dies are cut or diced from the wafer,then packaged as integrated circuits. One skilled in the art would knowhow to dice wafers and package die to produce integrated circuits. Anyof the exemplary circuits or method illustrated in the accompanyingfigures, or portions thereof, may be part of an integrated circuit.Integrated circuits so manufactured are considered part of thisinvention.

An integrated circuit in accordance with the embodiments of the presentinvention can be employed in essentially any application and/orelectronic system in which buffers are utilized. Suitable systems forimplementing one or more embodiments of the invention include, but arenot limited, to personal computers, interface devices (e.g., interfacenetworks, high-speed memory interfaces (e.g., DDR3, DDR4), etc.), datastorage systems (e.g., RAID system), data servers, etc. Systemsincorporating such integrated circuits are considered part ofembodiments of the invention. Given the teachings provided herein, oneof ordinary skill in the art will be able to contemplate otherimplementations and applications.

In accordance with various embodiments, the methods, functions or logicdescribed herein is implemented as one or more software programs runningon a computer processor. Dedicated hardware implementations including,but not limited to, application specific integrated circuits,programmable logic arrays and other hardware devices can likewise beconstructed to implement the methods described herein. Further,alternative software implementations including, but not limited to,distributed processing or component/object distributed processing,parallel processing, or virtual machine processing can also beconstructed to implement the methods, functions or logic describedherein.

The embodiment contemplates a machine-readable medium orcomputer-readable medium containing instructions 902, or that whichreceives and executes instructions 902 from a propagated signal so thata device connected to a network environment 922 can send or receivevoice, video or data, and to communicate over the network 922 using theinstructions 902. The instructions 902 are further transmitted orreceived over the network 922 via the network interface device(s) 924.The machine-readable medium also contains a data structure for storingdata useful in providing a functional relationship between the data anda machine or computer in an illustrative embodiment of the systems andmethods herein.

While the machine-readable medium 902 is shown in an example embodimentto be a single medium, the term “machine-readable medium” should betaken to include a single medium or multiple media (e.g., a centralizedor distributed database, and/or associated caches and servers) thatstore the one or more sets of instructions. The term “machine-readablemedium” shall also be taken to include any medium that is capable ofstoring, encoding, or carrying a set of instructions for execution bythe machine and that cause the machine to perform anyone or more of themethodologies of the embodiment. The term “machine-readable medium”shall accordingly be taken to include, but not be limited to:solid-state memory (e.g., solid-state drive (SSD), flash memory, etc.);read-only memory (ROM), or other non-volatile memory; random accessmemory (RAM), or other re-writable (volatile) memory; magneto-optical oroptical medium, such as a disk or tape; and/or a digital file attachmentto e-mail or other self-contained information archive or set of archivesis considered a distribution medium equivalent to a tangible storagemedium. Accordingly, the embodiment is considered to include anyone ormore of a tangible machine-readable medium or a tangible distributionmedium, as listed herein and including art-recognized equivalents andsuccessor media, in which the software implementations herein arestored.

It should also be noted that software, which implements the methods,functions and/or logic herein, are optionally stored on a tangiblestorage medium, such as: a magnetic medium, such as a disk or tape; amagneto-optical or optical medium, such as a disk; or a solid statemedium, such as a memory automobile or other package that houses one ormore read-only (non-volatile) memories, random access memories, or otherre-writable (volatile) memories. A digital file attachment to e-mail orother self-contained information archive or set of archives isconsidered a distribution medium equivalent to a tangible storagemedium. Accordingly, the disclosure is considered to include a tangiblestorage medium or distribution medium as listed herein and otherequivalents and successor media, in which the software implementationsherein are stored.

Although the specification describes components and functionsimplemented in the embodiments with reference to particular standardsand protocols, the embodiment are not limited to such standards andprotocols.

The illustrations of embodiments described herein are intended toprovide a general understanding of the structure of various embodiments,and they are not intended to serve as a complete description of all theelements and features of apparatus and systems that might make use ofthe structures described herein. Many other embodiments will be apparentto those of skill in the art upon reviewing the above description. Otherembodiments are utilized and derived therefrom, such that structural andlogical substitutions and changes are made without departing from thescope of this disclosure. Figures are also merely representational andare not drawn to scale. Certain proportions thereof are exaggerated,while others are decreased. Accordingly, the specification and drawingsare to be regarded in an illustrative rather than a restrictive sense.

Such embodiments are referred to herein, individually and/orcollectively, by the term “embodiment” merely for convenience andwithout intending to voluntarily limit the scope of this application toany single embodiment or inventive concept if more than one is in factshown. Thus, although specific embodiments have been illustrated anddescribed herein, it should be appreciated that any arrangementcalculated to achieve the same purpose are substituted for the specificembodiments shown. This disclosure is intended to cover any and alladaptations or variations of various embodiments. Combinations of theabove embodiments, and other embodiments not specifically describedherein, will be apparent to those of skill in the art upon reviewing theabove description.

In the foregoing description of the embodiments, various features aregrouped together in a single embodiment for the purpose of streamliningthe disclosure. This method of disclosure is not to be interpreted asreflecting that the claimed embodiments have more features than areexpressly recited in each claim. Rather, as the following claimsreflect, inventive subject matter lies in less than all features of asingle embodiment. Thus the following claims are hereby incorporatedinto the detailed description, with each claim standing on its own as aseparate example embodiment.

The abstract is provided to comply with 37 C.F.R. § 1.72(b), whichrequires an abstract that will allow the reader to quickly ascertain thenature of the technical disclosure. It is submitted with theunderstanding that it will not be used to interpret or limit the scopeor meaning of the claims. In addition, in the foregoing DetailedDescription, it can be seen that various features are grouped togetherin a single embodiment for the purpose of streamlining the disclosure.This method of disclosure is not to be interpreted as reflecting anintention that the claimed embodiments require more features than areexpressly recited in each claim. Rather, as the following claimsreflect, inventive subject matter lies in less than all features of asingle embodiment. Thus the following claims are hereby incorporatedinto the Detailed Description, with each claim standing on its own asseparately claimed subject matter.

Although specific example embodiments have been described, it will beevident that various modifications and changes are made to theseembodiments without departing from the broader scope of the inventivesubject matter described herein. Accordingly, the specification anddrawings are to be regarded in an illustrative rather than a restrictivesense. The accompanying drawings that form a part hereof, show by way ofillustration, and without limitation, specific embodiments in which thesubject matter are practiced. The embodiments illustrated are describedin sufficient detail to enable those skilled in the art to practice theteachings herein. Other embodiments are utilized and derived therefrom,such that structural and logical substitutions and changes are madewithout departing from the scope of this disclosure. This DetailedDescription, therefore, is not to be taken in a limiting sense, and thescope of various embodiments is defined only by the appended claims,along with the full range of equivalents to which such claims areentitled.

Given the teachings provided herein, one of ordinary skill in the artwill be able to contemplate other implementations and applications ofthe techniques of the disclosed embodiments. Although illustrativeembodiments have been described herein with reference to theaccompanying drawings, it is to be understood that these embodiments arenot limited to the disclosed embodiments, and that various other changesand modifications are made therein by one skilled in the art withoutdeparting from the scope of the appended claims.

What is claimed is:
 1. A magnetically enhanced high-density plasmaapparatus comprising: a hollow cathode target assembly; an anodepositioned on top of the hollow cathode target assembly, thereby forminga gap between the anode and the hollow cathode target assembly; acathode magnet assembly; a row of magnets that generate a magnetic fieldin the gap and a magnetic field on a surface of the hollow cathodetarget assembly with the cathode magnet assembly such that magneticfield lines are substantially perpendicular to a surface of the hollowcathode target assembly; an electrode positioned adjacent to the row ofmagnets behind the gap; a pulse power supply coupled to the electrode;and a radio frequency (RF) power supply coupled to the hollow cathodetarget assembly, the RF power supply igniting and sustaining plasma inthe hollow cathode target assembly, a frequency and power of the RFpower supply being selected to increase at least one of a degree ofdissociation of feed gas molecules, degree of ionization of feed gasatoms, the pulse power supply generating a train of voltage pulses, apulse, frequency, duration, and amplitude of the train of negativevoltage pulses being selected to increase a degree of dissociation offeed gas molecules to form a layer from sputtering hollow cathode targetmaterial onto a substrate.
 2. The apparatus defined by claim 1, whereinthe RF power supply generates output voltage with a frequency in a rangeof about 1 MHz to 100 MHz.
 3. The apparatus defined by claim 1, furthercomprising: a substrate holder; and an RF substrate bias magneticallyenhanced high-density plasma power supply coupled to the substrateholder that generates a bias voltage on the substrate in a range ofabout −10 V to −2000 V.
 4. The apparatus defined by claim 3, furthercomprising an inductor coupled between the substrate holder and ground.5. The apparatus defined by claim 1, wherein the magnetic field in thegap is in a range of about 50 G to 5000 G.
 6. The magnetically enhancedhigh-density plasma apparatus as defined by claim 1, wherein the cathodemagnetic assembly is rotatable.
 7. The apparatus defined by claim 1,wherein the hollow cathode target assembly comprises at least one of B,C, Al, Si, P, S, Ga, Ge, As, Se, In, Sn, Sb, Te, I, Tl, Pb, Bi, Sc, Ti,Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Lu,Hf, Ta, W, Re, Os, Ir, Pt, Au, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy,Ho, Er, Tm, Yb, Be, Mg, Ca, Sr, Ba.
 8. The apparatus defined by claim 1,wherein the hollow cathode target assembly comprises at least one of B,C, Al, Si, P, S, Ga, Ge, As, Se, In, Sn, Sb, Te, I, Tl, Pb, Bi, Sc, Ti,Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Lu,Hf, Ta, W, Re, Os, Ir, Pt, Au, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy,Ho, Er, Tm, Yb, Be, Mg, Ca, Sr, Ba in combination with at least one ofO2, N2, F, Cl, H2.
 9. The apparatus defined by claim 1, wherein thepulse power supply generates voltage pulses with positive and negativeportions.
 10. The apparatus defined by claim 1, wherein the RF powersupply generates output voltage with a frequency in a range of about 1MHz to 100 MHz.
 11. The apparatus defined by claim 1, wherein the RFpower supply generates a negative bias voltage on the hollow cathodetarget assembly.
 12. A method of sputtering a layer on a substrate usingmagnetically enhanced high-density plasma, the method comprising:forming a gap between a hollow cathode target assembly and an anode ontop of the hollow cathode target assembly; generating a magnetic fieldin the gap such that magnetic field lines are substantiallyperpendicular to a surface of the hollow cathode target assembly;connecting a pulse power supply to an electrode positioned behind thegap; providing radio frequency (RF) power to the hollow cathode targetassembly that ignites and sustains volume discharge in the hollowcathode target assembly; and generating a train of voltage pulsescomprising a frequency, duration, and amplitude selected to increase adegree of dissociation of feed gas molecules to form the layer fromsputtering hollow cathode target material onto the substrate
 13. Themethod defined by claim 12, further comprising connecting an inductorbetween a pole piece and ground.
 14. The method defined by claim 12,further comprising generating bias voltage on the substrate in a rangeof about −10 V to −2000 V.
 15. The method defined by claim 12, whereinthe magnetic field in the gap is in a range of about 50 G to 10000 G.16. The method defined by claim 12, wherein the hollow cathode targetassembly comprises at least one of B, C, Al, Si, P, S, Ga, Ge, As, Se,In, Sn, Sb, Te, I, Tl, Pb, Bi, Sc, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y,Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Lu, Hf, Ta, W, Re, Os, Ir, Pt, Au,La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Be, Mg, Ca, Sr,Ba.
 17. The method defined by claim 12, wherein the hollow cathodetarget assembly comprises at least one of B, C, Al, Si, P, S, Ga, Ge,As, Se, In, Sn, Sb, Te, I, Tl, Pb, Bi, Sc, Ti, Cr, Mn, Fe, Co, Ni, Cu,Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Lu, Hf, Ta, W, Re, Os, Ir,Pt, Au, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Be, Mg,Ca, Sr, Ba in combination with at least one of O2, N2, F, Cl, H2. 18.The method defined by claim 12, wherein the pulse power supply generatesvoltage pulses with positive and negative portions.
 19. The methoddefined by claim 12, wherein the RF power generates output voltage witha frequency in a range of about 1 MHz to 100 MHz.
 20. The method definedby claim 12, wherein the RF power generates a negative bias voltage onthe hollow cathode target assembly.